Catalyst for producing maleic anhydride

ABSTRACT

A catalyst for, and method of, producing a reaction product predominantly of maleic anhydride, that is a product of reaction containing a ratio of maleic to citraconic anhydrides of at least 25 to 1, respectively, and preferably greater than about 100 to 1, respectively, by reacting a feed stream consisting of oxygen or an oxygen-containing gas and an organic C 5  feed predominantly of piperylene and dicyclopentadiene, and preferably predominantly dicyclopentadiene, at bath temperatures of from about 360° to about 450° C. over a catalyst comprising a mixture of 25 to 60 weight percent titanium oxide (TiO 2 ), 5 to 40 weight percent molybdenum oxide (MoO 3 ) and 30 to 60 weight percent vanadium oxide (V 2  O 5 ) on an alpha alumina or alumina-silica carrier having less than about one square meter per gram (&lt;1 m 2  /g) surface area.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional, of application Ser. No. 828,409, filed Aug. 29, 1977, now U.S. Pat. No. 4,113,745.

BACKGROUND OF THE INVENTION

The oxidation of various organic compounds to prepare maleic and citraconic acid, while well documented in the literature, is abstracted here.

Conover in U.S. Pat. No. 2,079,490 (1937) disclosed the oxidation of cyclopentadiene and polymeric cyclopentadiene to maleic anhydride over any good catalyst for oxidation of organic materials to form carboxylic acids. The metals of the fifth and sixth group of the Periodic Table were disclosed and vanadium oxide on a support was illustrated.

Milas et al. in U.S. Pat. No. 2,136,144 disclose the oxidation of naphthenes over similar catalysts, viz., elements of the fifth and sixth groups of the Periodic System, specifically, vanadium, bismuth, molybdenum, tungsten, etc., supported on an inert carrier. Yields of maleic acid of 10 to 20.5 percent were reported.

Faith and Dendurent, Refiner & Natural Gasoline Manufacturer, Vol. 18, No. 10, Oct. 1939, pp. 61-64, disclosed the conversion of amylene to maleic anhydride over a vanadium pentoxide catalyst. C₆₋₈ olefinic hydrocarbons were reported to give even better yields than amylene.

Numerous patents have issued since 1939 disclosing specific catalyst composition reporting the results in preparing maleic and citraconic acids and anhydrides, to wit: U.S. Pat. Nos. 2,649,477; 2,719,853; 3,086,026; 3,106,569; 3,156,705; 3,156,706; 3,156,707; 3,366,648; and 3,464,930 to list but a few. U.S. Pat. No. 3,086,026 disclosed a V₂ O₅ /MoO₃, ratio of 1 to 1 to 1 to 8, respectively, with 0.2 to 1.25 percent P₂ O₅ and 60-80 percent TiO₂ on a support. U.S. Pat. No. 3,106,569 disclosed a 50-90 atomic percent vanadium, 5-45 at. percent Mo and 2-30 at. percent Ti on an inert support. Skinner & Tieszen (1961) reported an improved catalyst of 3V/9Mo/1P on SiO₂ gel and Mitsubishi Chemical Industries has disclosed a V-Mo-P on SiO₂ and a V-P on SiO₂ as suitable catalysts.

BRIEF DESCRIPTION OF THE INVENTION

An especially prepared C₅ hydrocarbon stream containing predominantly a mixture of cis- and trans-piperylene and dicyclopentadiene and co-dimers; that is a C₅ stream which has been distilled to remove the components boiling below isoprene and all or a major portion of the isoprene, and more preferably a feed stream composed of over 90 percent dicyclopentadiene and co-dimers, the remainder being benzene and heavies, is oxidized with oxygen or an oxygen-containing gas over a catalyst which is a 3 to 20 weight percent of a mixture of 30 to 60 weight percent vanadium oxide, 5 to 40 weight percent molybdenum oxide and 25 to 60 weight percent titanium oxide on an alpha alumina or alumina-silica support having a surface area of less than one square meter per gram (<1 m² /g). Exemplified in the Examples are catalyst wherein the ratio of V/Mo/Ti is in the range of 30 to 50 weight percent Ti and said mixture of V/Mo/Ti oxides is from 7 to 15 weight percent of the weight of said oxides and said alumina-silica carrier as well as a catalyst wherein said ratio of V/Mo/Ti is specifically exemplified as 40/15.2/44.8 and said oxides are present in admixture of 11.4 weight percent of said oxides and carrier.

The catalyst is prepared by impregnating the support with a mixture of aqueous solutions of the salts of the active ingredients, drying and calcining the so-prepared catalyst at about 500° C. for at least two hours.

The especially prepared feeds for use in accordance with the present invention are those in which isoprene and its precursors, monoolefins and saturates, and lights have been substantially removed and cyclopentadiene has been converted into dicyclopentadiene and its codimers. Three techniques to achieve this are illustratively described in FIGS. 1, 2 and 3 of the drawings. In FIG. 1 a crude C₅ stream is subjected to heat-soaking for about 8 to 32 hours at about 80° to 100° C. during which time dimerization occurs, thereafter the heat-soaked product if not used as feed, is distilled to remove isoprene and light hydrocarbons boiling below isoprene. The bottoms from this distillation is suitable as a feed for the present process and contains predominantly dicyclopentadiene, its co-dimers and piperylene. This product may be further distilled to separate the dicyclopentadiene and its co-dimers from the piperylene and the dicyclopentadiene used as a preferred feed in accordance with the present invention. FIG. 2 shows an alternative procedure to obtaining a de-lighted heat-soaked product which can be used as a feed or which can be further distilled to obtain a dicyclopentadiene/co-dimer fraction which can be used as a feed and an overhead which can further be separated into its predominant fractions. Finally, as shown in FIG. 3, is a further alternative procedure for obtaining a heat-soaked and de-lighted heat-soaked feed as well as a dicyclopentadiene/co-dimer concentrate for use as a feed. An alternative method, not shown is to heat soak the crude C₅ stream as in all other schemes shown and hereabove described, then distill the heat soaked material to remove substantially all of the components boiling below dicyclopentadiene and co-dimers, that is, remove the mono- and diolefins including isoprene and the piperylenes to obtain as a bottom cut the dicyclopentadienes and co-dimers. This bottom cut may be used as a starting material for the present invention or it may be combined with the piperylene cut subsquently obtained during the recovery of isoprene from the distillations of the overhead from this distillation. In practice the overhead is subjected to extractive distillation to separate the monoolefins and saturates from the diolefins (mainly isoprene and piperylenes) which latter, the diolefins, are further distilled to recover the isoprene. The bottoms cut from this distillation, predominantly the piperylenes, are useful per se in accordance with the present process or may be combined with the bottom cut of the first distillation of this alternative process and the mixture used as a starting material for the present invention. The various compositions obtained by treatment in accordance with the procedure of FIG. 3 are representatively set forth in the following table.

                  TABLE I                                                          ______________________________________                                         FEEDSTOCK COMPOSITIONS                                                                  Crude C5  Crude C5.sup.1                                                       Heat-     Heat-Soaked                                                                               Pipery- DCPD                                              Soaked    De-lighted lene.sup.2                                                                             Concen-                                  Components                                                                              (C5-HS)   (C5-HSDL)  + DCPD  trate.sup.3                              ______________________________________                                         Isopentane                                                                              10.0      .2                                                          3-Methyl-                                                                      Butene-1 .7        .1                                                          n-Pentane                                                                               16.2      .2                                                          Pentene-1                                                                               2.7       5.2        1.5                                              2-Methyl-                                                                      Butene-1 4.3       .7                                                          cis-trans-                                                                     Pentene-2                                                                               2.5       7.2        2.2                                              2-Methyl-                                                                      Butene-2 2.1       2.2        1.4                                              Isoprene 17.4      15.6       3.4                                              Cyclopentene                                                                            3.7       10.9       14.5                                             cis-,trans-                                                                    Piperylene                                                                              9.9       25.4       24.5                                             Cyclopenta-                                                                    diene    2.6       3.4        1.4                                              Benzene  .9        1.8                1.0                                      DCPD and                                                                       codimers 17.0      21.0       48.0    95.5                                     Heavies            2.5        2.0     3.5                                      ______________________________________                                          .sup.1 Derived by distillation of crude C.sub.5 fraction after heatsoakin      (C5HSDL).                                                                      .sup.2 Derived by distillation of C5HSDL cut.                                  .sup.3 Derived by distillation of piperylene + DCPD cut.                 

DETAILED DESCRIPTION OF THE INVENTION Catalyst Preparation

General Procedure:

Vanadium pentoxide (V₂ O₅) was reduced with oxalic acid dihydrate in water on a steam bath and ammonium molybdate ((NH₄)₆ Mo₇ O₂₄.4H₂ O) was dissolved in water. The two solutions were combined and heated (70°-90° C.) overnight. Titanium oxide (TiO₂) was added, the mixture stripped for 2 hours on a steam bath and then sprayed onto alumina-silica spheres, Norton SA 5205, 3/16" to 3/8", while tumbling the spheres. The spheres were then dried at room temperature in an air stream, then at 130° C. Thereafter, the spheres were heated to 400° C. at a rate of 100° C. per hour. Finally, the spheres were calcined at 500° C. for 2 hours, cooled, sieved to remove the fines, the catalyst loading determined and then tested in the laboratory according to the following General Oxidation Procedure.

Process Parameters

General Oxidation Procedure:

A U-tube, 5/8" O.D., ca 1/2" I.D. stainless steel, was immersed in a salt bath. About 12 cm³ of a catalyst, prepared as above, crushed and screened to -5 to +12 screen, was introduced into the upflow side of the tube. A 1/8" thermowell was positioned in the catalyst bed. The reaction mixture entered the downflow side of the tube. Liquid feed was metered with capillary tubing; gas feed with a gas flow meter. Products were condensed at 5°-15° C. and water-scrubbed. The combined products were analyzed by liquid chromatography for maleic anhydride and citraconic anhydride. The hydrocarbon conversion was essentially complete.

The following table illustrates the results employing the catalysts of the present invention in Examples 1, 2, 3, 4 and 6 while Examples 5 and 7-10 represent results using prior art catalysts. The yield is expressed in weight percent based on total feed fed into the reactor. Liquid flows were in the range of up to 6 gm/hr, care being taken to maintain concentrations outside the explosive limits in air. Air flows were from 72 to 144 liters per hour. Experimental results are reported in Table II as follows:

First line--

% loading (catalyst composition) on Norton SA 5205 alumina-silica spheres crushed to -5 to +12 screen.

Second line--

Feedstock origin, % by volume hydrocarbon in air, gas hourly space velocity hr⁻¹, bath temperature in °C. and yields as percent of maleic anhydride and citraconic anhydride, based on weight percent hydrocarbon fed.

The above procedure was employed to react the below-enumerated feeds with air over the catalyst. The results are tabulated below.

                  TABLE II                                                         ______________________________________                                         SUMMARY OF OXIDATION RUNS                                                                               Bath                                                  Feed             GHSV    Temp.   Yields                                        Ex.  (Origin)   (% Vol)  (hr.sup.-1)                                                                          °C.                                                                           % MA  % CA                                ______________________________________                                         1    14.6%(70%[2V/l Mo] + 30% TiO.sub.2)SA 5205                                C.sub.5 -HSDL                                                                              1.01     6000    406   50.6  7.3                                   DCPD Conc.  .66      8000    412   78.0  0.5                                   Pip/DCPD    .75      8000    417   64.9  1.9                                   2    11.4%(60%[4.67V/l Mo] + 40% TiO.sub.2)SA 5205                             C.sub.5 -HSDL                                                                              .95      8000    398   51.1  7.7                                   DCPD Conc.  .70      8000    428   80.4  0.5                                   Pip/DCPD    .73      8000    425   67.3  2.6                                   3    18.9(50%[ 4.67V/l Mo] + 50% TiO.sub.2)SA 5205                             C.sub.5 -HSDL                                                                              .97      8000    384   51.7  8.2                                   DCPD Conc.  .65      8000    408   81.1  0.0                                   Pip/DCPD    .81      8000    410   64.8  2.0                                   4    10.3%(70%[9V/l Mo]/0.45 P + 30% TiO.sub.2)SA 5205                         C.sub.5 -HSDL                                                                              .84      12000   422   49.3  7.4                                   Pip/DCPD    .82      12000   421   60.0  7.8                                   DCPD Conc.  .86      12000   436   68.4  0.2                                   Crude C.sub.5                                                                              1.22     12000   422   24.5  10.0                                  5    10.86%[4.67V/l Mo]SA 5205                                                 C.sub.5 -HSDL                                                                              .89      6000    443   50.8  6.0                                   6    12.6%[50%(4.67V/l Mo) + 50% TiO.sub.2 ]SA 5205                            DCPD Conc.  1.02     6000    430   75.7  0.0                                   Pip/DCPD    0.85     8000    417   62.5  2.3                                   7    7.9%[80%(4.67 V/l Mo) + 20% TiO.sub.2 ]SA 5205                            DCPD Conc.  1.0      6000    435   75.6  0.0                                   Pip/DCPD    0.8      8000    433   61.4  1.5                                   8    18.6%[30%(4.67V/l Mo) + 70% TiO.sub.2 ]SA 5205                            DCPD Conc.  1.03     6000    422   70.3  0.0                                   Pip/DCPD    .79      8000    416   64.1  2.4                                   9    6.68%(4.67V/l Mo)SA 5205                                                  DCPD Conc.  1.03     6000    438   65.9  0.3                                   Pip/DCPD    .82      8000    454   57.1  1.7                                   10   10.9%[9V/l Mo]SA 5205                                                     C.sub.5 HSDL                                                                               .89      12000   428   48.9  6.9                                   DCPD        1.03     10000   399   75.9  0.0                                   Piperylene  .99      12000   408   51.0  5.1                                   ______________________________________                                    

Additional experiments were run employing catalysts of four references. The results are set forth below:

                  TABLE III                                                        ______________________________________                                         SUMMARY OF OXIDATION RUNS                                                                               Bath                                                  Feed             GHSV    Temp.   Yields                                        Ex.  (Origin)   (% Vol)  (hr.sup.-1)                                                                          °C.                                                                           % MA  % CA                                ______________________________________                                         1    Halcon benzene oxidation catalyst, British 1371653 (74)                        10.29%(1.0 V.sub.2 O.sub.5 /.87 MoO.sub.3 /0.083 B.sub.2 O.sub.3               /0.096 Na.sub.2 O/                                                             0.028 P.sub.2 O.sub.5 /0.042 CoO.sub.3)SA 5205                            C.sub.5 -HSDL                                                                              1.0      8000    437    43.7 4.8                                   2    JAP. DCPD/CPD Catalyst, Jap. Pat. Publ. 21,093/1973                            8.35%(1.0 V.sub.2 O.sub.5 /0.2 MoO.sub.3 /0.02 Na.sub.2 O/0.01                 P.sub.2 O.sub.5 /                                                              0.03 NiO)SA 5205                                                          C.sub.5 -HSDL                                                                              .95      6000    447   51.1  4.8                                   95% DCPD    .74      6000    438   76.9  0.0                                   DCPD Conc.  .74      6000    447   71.7  0.0                                   Pip/DCPD    .71      6000    446   54.1  2.2                                   3    Monsanto Example 3 U.S. 3,106,569(63), Benzene                                 7.25%[92.4%(8.1 V/l Mo) + 7.6% TiO.sub.2 ]SA 5205                          DCPD Conc. 1.02     6000    428    72.9 0.0                                   Pip/DCPD    .79      8000    430   59.1  1.0                                   4    BASF, Example 3 U.S. 3,086,026(63), Benzene                                    100%[35.8%(1.2 V/l Mo/0.08P) + 64.2% TiO.sub.2 ]                               unsupported                                                               DCPD Conc.  .95      6000    431   58.7  0.0                                   Pip/DCPD    .81      8000    400   59.7  0.8                                   ______________________________________                                    

Data obtained employing the present invention compared to the most closely related prior art known at the time the invention was made illustrates the superior results obtainable employing the present invention, and establishes the necessity for the presence of titanium oxide as a component of the catalyst even when employing the most advantageous feedstock.

    __________________________________________________________________________     Effect of TiO.sub.2 on Yields to MA from C.sub.5 (HSDL), Piperylene/DCPD       and DCPD Concentrate                                                                                                  DCPD                                                               C.sub.5 (HSDL)                                                                       Pip/DCPD                                                                             Concentrate                             TiO.sub.2 Concentration                                                                              Example                                                                             Ma CA MA CA MA  CA                                  __________________________________________________________________________     0% (1) 6.68% (4.67/1, V/Mo)                                                                          12   -- -- 57.1                                                                              1.7                                                                               65.9                                                                               0.3                                    Japan Pat. Publ. 21,093(73)                                                                       2    51.1                                                                              4.8                                                                               54.1                                                                              2.2                                                                               71.7                                                                               0.0                                    Halcon British 1,371,653                                                                          1    43.7                                                                              4.8                                                                               -- -- --  --                                     (7.25% Monsanto)                                                               (Example 3, U.S. Pat. No. 3,106,569)                                                              13   -- -- 59.1                                                                              1.0                                                                               72.9                                                                               0.0                                 20%                                                                               (1) 7.9% (4.67/1, V/Mo)                                                                           7    -- -- 61.4                                                                              1.5                                                                               75.6                                                                               0.0                                 30%                                                                               (1) 14.6% (4.67/1, V/Mo)                                                                          1    50.6                                                                              7.3                                                                               64.9                                                                              1.9                                                                               78.0                                                                               0.5                                 40%                                                                               (1) 11.4% (4.67/1, V/Mo)                                                                          2    51.1                                                                              7.7                                                                               67.3                                                                              2.6                                                                               80.4                                                                               0.5                                 50%                                                                               (1) 13.9% (4.67/1, V/Mo)                                                                          3    51.7                                                                              8.2                                                                               64.8                                                                              2.0                                                                               81.1                                                                               0.0                                    (64.2% BASF)                                                                   (Example 3, U.S. Pat. No. 3,086,026)                                                              14   -- -- 59.7                                                                              0.8                                                                               58.7                                                                               0.0                                 70%                                                                               (1) 18.6% (4.67/1, V/Mo)                                                                          11   -- -- 64.1                                                                              2.4                                                                               70.3                                                                               0.0                                 __________________________________________________________________________      (1) Catalyst prepared by Applicants with indicated % of a mixture of 4.67      to 1 vanadium to molybdenum on a support with indicated TiO.sub.2              percentage.                                                                    These data illustrate that high (>60+) and low (<30-) TiO.sub.2 contents       give poorer yields to MA. This is particularly evident with DCPD               Concentrate as feed, but can also be observed with Piperylene/DCPD.      

The effect of the presence of titanium oxide is further illustrated in the fact that the presence of >20 and <60 weight percent of titanium oxide based on the total V₂ O₅, MoO₃ and TiO₂ in the catalyst permits the use of slightly lower temperatures than catalysts without titanium oxide or greater than 60 percent titanium oxide without appreciable loss of conversion or yield of maleic anhydride to citraconic acid.

    ______________________________________                                         Effect of TiO.sub.2 on Reaction Temperature                                           DCPD Conc.  Ratio    Pip/DCPD  Ratio                                    % TiO.sub.2                                                                           Bath Temp. °C.                                                                      MA/CA    Bath Temp. °C.                                                                    MA/CA                                    ______________________________________                                         0      438          65.9/.3 454       57.1/1.7                                 20     435         75.6/0   433       61.4/1.5                                 50     430         75.7/0   417       62.5/2.3                                 70     422         70.3/3.0 416       64.1/2.4                                 7.25   428         72.9/0   430       57.1/1.7                                 ______________________________________                                     

We claim:
 1. A catalyst suitable for oxidation of dicyclopentadiene and piperylene/dicyclopentadiene mixtures to produce maleic anhydride as the predominant product which comprises a mixture of vanadium oxide, molybdenum oxide, and titanium oxide supported on an inert carrier in an amount to supply from 3-20 weight percent of the mixture having a ratio of V₂ O₅ /MoO₃ /TiO₂ of 25 to 60 weight percent V₂ O₅, 5 to 40 weight percent MoO₃, 30 to 60 weight percent TiO₂, said carrier being α-Al₂ O₃ or alumina-silica having a surface area of less than about 1 square meter per gram.
 2. The catalyst of claim 1 wherein the ratio of V/Mo/Ti is in the range of 30 to 50 weight percent V, 10 to 30 weight percent Mo, 35 to 50 weight percent Ti and said mixture of V/Mo/Ti oxides is from 7 to 15 weight percent of the weight of said oxides and said alumina-silica carrier.
 3. The catalyst of claim 1 wherein said ratio of V/Mo/Ti is 40/15.2/44.8 and said oxides are present in admixture of 11.4 weight percent of said oxides and carrier. 